CN108424206A - Flyash acid system residue of aluminum-extracted prepares the method containing silicon composite fertilizer and the utilization method containing silicon composite fertilizer and flyash - Google Patents
Flyash acid system residue of aluminum-extracted prepares the method containing silicon composite fertilizer and the utilization method containing silicon composite fertilizer and flyash Download PDFInfo
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- CN108424206A CN108424206A CN201810564662.XA CN201810564662A CN108424206A CN 108424206 A CN108424206 A CN 108424206A CN 201810564662 A CN201810564662 A CN 201810564662A CN 108424206 A CN108424206 A CN 108424206A
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- calcium
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- silicon
- flyash
- aluminum
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D3/00—Calcareous fertilisers
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D5/00—Fertilisers containing magnesium
Abstract
The present invention relates to the utilization fields of flyash acid system residue of aluminum-extracted and flyash, disclose flyash acid system residue of aluminum-extracted and prepare the method containing silicon composite fertilizer and the utilization method containing silicon composite fertilizer and flyash.This method includes：(1) in the presence of NaOH solution, flyash acid system residue of aluminum-extracted and the source of manure are mixed into slurries, and carry out heating reaction, wherein the source of manure is calcium source and/or magnesium source；(2) reaction product that step (1) obtains is separated by solid-liquid separation, gained filter cake obtains silico-calcium composite fertilizer, silicon magnesium compound fertilizer or silicon-calcium-magnesium compound fertilizer after being granulated, drying.This method can simplify preparation manipulation, avoid the separation of solid and liquid operation of sodium metasilicate, reduce the loss of nutrient silicon, calcium, magnesium, and Na residual rates are low in obtained composite fertilizer.
Description
Technical field
The present invention relates to the utilization fields that flyash acid system carries aluminium slag and flyash, and in particular, to flyash acid system carries
Residue of aluminum prepares the method containing silicon composite fertilizer and the utilization method containing silicon composite fertilizer and flyash.
Background technology
Aluminous fly-ash is a kind of novel bauxite resource specific to China, about 10,000,000,000 tons of aluminium oxide of Prospective resources.It is high
The utilization of aluminium powder coal ash can greatly alleviate the problem of China's bauxite resource shortage." a step acid is molten " method is so far one
The ideal aluminous fly-ash of kind extracts aluminium oxide method, but often produces 100 tons of Al2O3By about 130-150 tons of high silicon of discharge
Solid slag -- " residue of aluminum-extracted pulverized fuel ash " is commonly called as white clay in industry.
Currently, the utilization of residue of aluminum-extracted pulverized fuel ash is concentrated mainly on silicon systems product (waterglass, white carbon, silicon powder etc.) system
Standby, basic building materials (cement, ceramic tile, steam-pressing brisk etc.) manufacture, and for producing the fields such as heat preservation, refractory material.More than but
There is different degrees of contradiction in application direction, cause white between product economy added value, market capacity and consumption efficiency
Mud overall utilization rate is relatively low.According to relevant regulations, the solid waste using aluminous fly-ash production alumina system is created,
Comprehensive utilization ratio must reach 96% or more.The current existing various utilization rates utilized of white clay are far from this index is reached, directly
It connects and limits application and popularization that aluminous fly-ash carries aluminum technology.Thus, the high level of white clay, efficient consumption technology are urgently developed.
In international soil circle, siliceous fertilizer is listed in the fourth-largest element fertilizer after nitrogen, phosphorus, potassium.National soil measurement formula
Silica whether will be lacked as technical standard.Siliceous fertilizer has become a kind of new-type fertilizer of 21 century China.Currently, China
Lack the 50-80% or more that tripoli earth accounts for total area under cultivation.By taking rice as an example, the area of the long-term rice cultivation in China is up to more than 3,333 ten thousand
Hectare lacks tripoli earth and accounts for 50% or more.If whole Applying silicon fertilizers, based on volume increase 10%, only this item should can increase production 100 every year
Ten thousand tons of paddy, the production and application for promoting siliceous fertilizer have obviously social and economic benefit.Siliceous fertilizer industry future is considerably long
One period will be in ascent stage, and the market space is huge, competitive pressure very little.In addition, calcium, magnesium are also growth and development of plants institute
Required moderate-element.Si, Ca, Mg are supplemented for soil, can be developed to crop production has collaboration facilitation.
CN1923764A discloses a kind of silicon, calcium and magnesium fertilizer, wherein constitutes the raw material and weight percent of silicon-calcium-magnesium fertilizer
It is water-hardened steel slag and 60-70 %, magnesia unslacked 4-12%, white residue 10-20%, dilute sulfuric acid 15-20%, brine 1-3% than content.Specifically
Preparation method be water quenching slag, light calcined magnesia, white residue etc. mixs in proportion after plus dilute sulfuric acid at 135 DEG C acid burning
20min is to obtain acid product system in acid condition.
CN101591197A discloses a kind of method preparing calcium silicate fertilizer using pre-desiliconizing with high alumina fly ash, including (1) will
Raw material aluminous fly-ash is added sodium hydroxide solution and carries out alkali soluble reaction；(2) sodium silicate solution generated to alkali soluble reaction carries out
It is separated by filtration, dispensing of the filter cake desiliconization flyash as extraction aluminium oxide；(3) add stone into the sodium silicate solution after being separated by filtration
Grey breast precipitation reaction is simultaneously separated by filtration, and filter cake is calcium silicates, and filtrate is sodium hydroxide solution, sodium hydroxide solution return to step
(1) it recycles；(4) filter cake calcium silicates is dried, is levigate, silico-calcium fertilizer product is made.The used process route of this method
The step of (2) be related to the separation of solid and liquid of sodium metasilicate.And sodium silicate solution (being commonly called as " waterglass ") has high viscosity characteristic, when separation
Operating difficulties, filter loss rate are excessively high.Although heat preservation filtering (use 90 DEG C at filter) can be taken, increase filter pressure or
Filter plant is improved, but increases operation difficulty or equipment cost, raises the manufacturing cost containing silicon composite fertilizer.
CN107188766A discloses a kind of coal ash for manufacturing for the method for silicon composite fertilizer, including：(1) fly ash in electric power plant is passed through
Flour mill is handled to 150-200 mesh；(2) flyash after crushing is fully reflected with dilute hydrochloric acid, filters out siliceous filter residue, by this
It is spare after siliceous filter residue drying；(3) by the filtrate in step (2) at 100-150 DEG C evaporative crystallization, obtain chloride containing calcium, chlorine
Change the solid mixture of magnesium crystal；(4) the siliceous filter residue of drying of step (2) is fully reacted with sodium hydroxide solution, is contained
Sodium silicate liquid mixture；(5) liquid mixture containing sodium metasilicate of step (4) is sprayed onto to be granulated on comminutor bed of material and is prepared
Silicon composite fertilizer, the material on bed of material includes humic acid, nitrogenous fertilizer, phosphate fertilizer, potash fertilizer, bentonite and trace-element fertilizer；Wherein, contain
The weight percent difference of sodium silicate liquid mixture, humic acid, nitrogenous fertilizer, phosphate fertilizer, potash fertilizer, bentonite and trace-element fertilizer
For；5-10%, 5-10%, 30-35%, 20-35%, 10-25%, 0.5-1%, 0.5-1%.The preparation side containing silicon composite fertilizer
Method is substantially the mechanical compound of multiple nutritional components.In addition silicon source is sodium silicate solution, Na2O/SiO2Mass ratio >=1, this
The strong basicity Na more than a unit will be introduced while meaning to provide effective silicon of a unit to soil2O, fertilising knot
There is aggravation alkalization of soils or saliferous risk in fruit.
As can be seen that the prior art is being raw material using flyash, siliceous fertilizer and siliceous multiple is prepared using NaOH alkali soluble systems
During Hefei, existing technological deficiency is：(1) sodium element excessively introduces, i.e., in the case of the identical equivalent of offer effective silicon,
A large amount of Na elements are synchronized introducing, and the ratio between soluble sodium and effective silicon cross Na2O/SiO2It is excessively high；(2) it is related to sodium metasilicate to produce with solid phase
When object is separated by solid-liquid separation, easily cause the filter loss of Si, Na excessive, or cause the effective silicon of operating condition, energy consumption cost, product
The deterioration of the indexs such as content.
Invention content
The purpose of the invention is to overcome drawbacks described above, provides flyash acid system residue of aluminum-extracted and prepare containing silicon composite fertilizer
Method and utilization method containing silicon composite fertilizer and flyash.
In order to achieve the above-mentioned object of the invention, a kind of flyash acid system residue of aluminum-extracted of first aspect present invention offer is prepared siliceous
The method of composite fertilizer, including：
(1) in the presence of NaOH solution, flyash acid system residue of aluminum-extracted and the source of manure are mixed into slurries, and heat anti-
It answers, wherein the source of manure is calcium source and/or magnesium source；
(2) reaction product that step (1) obtains is separated by solid-liquid separation, gained filter cake obtains silico-calcium after being granulated, drying
Composite fertilizer, silicon magnesium compound fertilizer or silicon-calcium-magnesium compound fertilizer.
Preferably, when the source of manure is calcium source, the flyash acid system residue of aluminum-extracted is with SiO2Meter, the NaOH solution with
In terms of CaO, the weight ratio of flyash acid system residue of aluminum-extracted, NaOH solution and calcium source is 1 for NaOH meters, the calcium source：1.3-1.7：
0.6-0.8。
Preferably, when the source of manure is calcium source and magnesium source, the flyash acid system residue of aluminum-extracted is with SiO2Meter, the NaOH
Solution in terms of NaOH, the calcium source in terms of CaO, the magnesium source is in terms of MgO, flyash acid system residue of aluminum-extracted, NaOH solution, calcium source
Weight ratio with magnesium source is 1：1.3-1.7：0.1-0.6：0.4-0.04.
Preferably, when the source of manure is magnesium source, the flyash acid system residue of aluminum-extracted is with SiO2Meter, the NaOH solution with
In terms of MgO, flyash acid system residue of aluminum-extracted, NaOH solution and the weight ratio in magnesium source are 1 for NaOH meters, the magnesium source：1.5-1.8：
0.5-0.7。
Preferably, heating reaction temperature is 90-160 DEG C, and heating reaction pressure is normal pressure, and the heating reaction time is 1-5h.
Preferably, this method further includes washing the filter cake, then by obtained by the washing containing soda-wash water and
Filtrate obtained by the separation of solid and liquid merges together the concentrated rear NaOH solution for returning to addition step (1) again.
Preferably, after the washing, sodium oxide content is 8 weight % or less in the filter cake.
Preferably, viscosity of the reaction product at 25 DEG C described in step (2) is 1-4mPas.
It is obtained containing silicon composite fertilizer that second aspect of the present invention provides a kind of method of the present invention, wherein described siliceous compound
Solubility Na in fertilizer2O content is 6 weight % hereinafter, described containing silicon composite fertilizer is silico-calcium composite fertilizer, silicon magnesium compound fertilizer or silicon-calcium-magnesium
Composite fertilizer.
Third aspect present invention provides a kind of utilization method of flyash, including：Flyash progress acid system is carried aluminium to obtain
Silicon is prepared in the method for the flyash acid system residue of aluminum-extracted through the invention by aluminium oxide and flyash acid system residue of aluminum-extracted
Calcium composite fertilizer, silicon magnesium compound fertilizer or silicon-calcium-magnesium compound fertilizer.
Through the above technical solutions, method provided by the invention can significantly simplify technological process, and avoid sodium metasilicate
Separation of solid and liquid operation, reduce the loss of nutrient, element silicon filter loss rate is less than 1.0 weight %.And what is obtained answers
Na residual rates are low in Hefei, available silicon content 21-38 weight % in obtained composite fertilizer, effective content of magnesium 5-40%, effective calcium
Content 5-40%；The harmful solubility Al of agricultural2O3Content is less than 8%, soluble Na2O content is less than 6%.
It is recycled containing alkali waste water in method provided by the invention, water consumption and the minimum of sewage discharge may be implemented
Change.Without secondary solid waste discharge in method provided by the invention.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Attached drawing is to be used to provide further understanding of the present invention, an and part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the method flow diagram provided by the invention for preparing silico-calcium composite fertilizer；
Fig. 2 is the method flow diagram provided by the invention for preparing silicon-calcium-magnesium compound fertilizer；
Fig. 3 is the method flow diagram provided by the invention for preparing silicon magnesium compound fertilizer.
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The first aspect of the present invention provides a kind of method of the flyash acid system residue of aluminum-extracted preparation containing silicon composite fertilizer, including：
(1) in the presence of NaOH solution, flyash acid system residue of aluminum-extracted and the source of manure are mixed into slurries, and heat anti-
It answers, wherein the source of manure is calcium source and/or magnesium source；
(2) reaction product that step (1) obtains is separated by solid-liquid separation, gained filter cake obtains silico-calcium after being granulated, drying
Composite fertilizer, silicon magnesium compound fertilizer or silicon-calcium-magnesium compound fertilizer.
In the present invention, flyash acid system residue of aluminum-extracted mainly contains：SiO2、Al2O3And TiO2。SiO2Content be about 70-
80 weight %, Al2O3Content be about 10-15 weight % and TiO2Content be about 3-8 weight %.Such as the Shenhua Inner Mongol is accurate
Ge Er flyash acid system residue of aluminum-extracted, wherein SiO2Content be about 78.7 weight %, Al2O3Content be about 13.4 weight %
And TiO2Content be about 5.2 weight %.Moreover, further show flyash acid system residue of aluminum-extracted progress XRD analysis,
Al2O3Substantially with mullite (3Al2O3·SiO2) form exist, TiO2Carrier is anatase and rutile；There are about 85% Si
Exist as an amorphous form, remaining Si preservations are in mullite and quartz.
According to the present invention, a kind of specific implementation mode, flow as shown in Figure 1.Wherein, it is described when the source of manure is calcium source
Flyash acid system residue of aluminum-extracted is with SiO2Meter, the NaOH solution in terms of NaOH, the calcium source in terms of CaO, flyash acid system carries
The weight ratio of residue of aluminum, NaOH solution and calcium source is 1：1.3-1.7：0.6-0.8.
According to the present invention, another specific implementation mode, flow as shown in Figure 2.Wherein, the source of manure is calcium source and magnesium source
When, the flyash acid system residue of aluminum-extracted is with SiO2Meter, the NaOH solution in terms of NaOH, the calcium source in terms of CaO, the magnesium
In terms of MgO, flyash acid system residue of aluminum-extracted, NaOH solution, calcium source and the weight ratio in magnesium source are 1 in source：1.3-1.7：0.1-0.6：
0.4-0.04。
According to the present invention, another specific implementation mode, flow as shown in Figure 3.Wherein, when the source of manure is magnesium source, institute
Flyash acid system residue of aluminum-extracted is stated with SiO2Meter, the NaOH solution in terms of NaOH, the magnesium source in terms of MgO, flyash acid system
The weight ratio of residue of aluminum-extracted, NaOH solution and magnesium source is 1：1.5-1.8：0.5-0.7.
By above-mentioned three kinds of specific implementation modes, method provided by the invention may be implemented flyash acid system residue of aluminum-extracted with
The source of manure in the presence of NaOH directly it is heated reaction and produce silico-calcium composite fertilizer, silicon magnesium compound fertilizer or silicon-calcium-magnesium compound fertilizer.
This method, which can evade, generates sodium silicate solution intermediate product, and avoid the sodium silicate solution of more difficult progress is separated by filtration behaviour
Make, reduces the difficulty that entire technological process carries out.This method is there is no sodium metasilicate is generated, without the filtering point of sodium metasilicate
From, it is possible to reduce filter loss.
In the present invention, the NaOH concentration of the NaOH solution can be 10-20 weight %.
According to the present invention, the heating is reacted to complete flyash acid system residue of aluminum-extracted and silicon, the calcium in the source of manure, or
Person's silicon, calcium, magnesium or silicon, magnesium are subjected to chemical change and are combined to obtain accordingly containing silicon composite fertilizer.Preferably, heating reaction
Temperature is 90-160 DEG C, and preferably 90-150 DEG C, heating reaction pressure is normal pressure, and the heating reaction time is 1-5h, preferably 2-
5h.In the present invention, the heating reaction is carried out without pressurizeing, and normal pressure can be normal environment pressure when carrying out the heating reaction
Power under standard state, such as can be 0.1-0.2MPa.Normal pressure is gauge.
According to the present invention, the NaOH solution in step (1) can be used as catalyst to exist, and participate in chemical reaction but theoretically
It is not consumed, and NaOH can be separated and recovered by the obtained reaction product.Preferably, this method further includes by the filter
Cake is washed, then by merging together again through dense containing the filtrate obtained by soda-wash water and the separation of solid and liquid obtained by the washing
The NaOH solution that step (1) is added is returned after contracting.Raw material can be made full use of, and avoids the discharge of lye, is avoided secondary
Pollution.NaOH recycles efficiency (η) can calculate the mass percent that Na elements use by the following method：[(step (1)
The absolute mass of Na elements in absolute mass-product of the Na elements of middle addition) be added in/step (1) Na elements it is absolute
Quality] × 100%.Process of the NaOH solution of recycling for step (1) meets the relationship above-mentioned that feeds intake.
According to the present invention, NaOH solution is not combined closely with obtained reaction product in the method provided, and is easy to pass through
General water washing operations remove sodium element in the filter cake, can reduce the content of sodium element in filter cake, reduce fertilising and give soil band
The negative effect come.Preferably, after the washing, sodium oxide molybdena sodium content is 8 weight % or less in the filter cake.
According to the present invention, this method can be to avoid the generation of sodium metasilicate, and the separation of solid and liquid in step (2) is more simple.This
It can reflect the complexity of separation of solid and liquid with the viscosity of reaction product described in step (2) in invention.Preferably, step (2)
Described in viscosity of the reaction product at 25 DEG C be 1-4mPas, preferably 1.2-3.8mPas.The reaction product has
Viscosity within this range, can be more easily separated by solid-liquid separation compared to sodium silicate solution.
It is obtained containing silicon composite fertilizer that second aspect of the present invention provides a kind of method of the present invention, wherein described siliceous compound
Solubility Na in fertilizer2O content is 6 weight % or less；The silicon composite fertilizer that contains is silico-calcium composite fertilizer, silicon magnesium compound fertilizer or silicon-calcium-magnesium
Composite fertilizer.Soluble Na2O refers to the Na that can be extracted by 0.5mol/L hydrochloric acid solutions2O mass accounts for the gross mass containing silicon composite fertilizer
Percentage, standard NYT2272-2012 may be used《The measurement of soil conditioner silicon magnesium calcium content》The middle side for measuring silicone content
Method.
In the present invention, through above-mentioned technical proposal, it is possible to reduce the solid-liquid point of sodium silicate solution must be carried out in the prior art
From and make the loss containing active principle in silicon composite fertilizer.The obtained content containing active principle in silicon composite fertilizer is high.By calculating,
The obtained available silicon content in silicon composite fertilizer that contains far surpasses 20% national standard up to 40%.
Third aspect present invention provides a kind of utilization method of flyash, including：Flyash progress acid system is carried aluminium to obtain
Silicon is prepared in the method for the flyash acid system residue of aluminum-extracted through the invention by aluminium oxide and flyash acid system residue of aluminum-extracted
Calcium composite fertilizer, silicon magnesium compound fertilizer or silicon-calcium-magnesium compound fertilizer.Flyash can be more effectively utilized, Commercial cultivation aluminium money therein is taken into account
Source.
Wherein, flyash can be the fine ash that catching is got off from the flue gas after the coal combustion that coal-burning power plant is discharged.It can be with
It is to mainly contain SiO2、Al2O3And TiO2。SiO2Content be about 20-40 weight %, Al2O3Content be about 45-60 weight %
And TiO2Content be about 1.5-4.5 weight %.Such as the flyash of power plant of China of Inner Mongol ancient country of Shenhua discharge, wherein SiO2Contain
Amount is about 32.43 weight %, Al2O3Content be about 50.42 weight % and TiO2Content be about 2.14 weight %.
Heretofore described acid system carries aluminium and method well known in the art may be used, and details are not described herein.
The present invention will be described in detail by way of examples below.
The viscosity of reaction product is measured by NDJ-8S type viscosimeters in embodiment and comparative example.Basic principle is rotor
Can be by the acting in opposition torque of liquid in rotary course in testing liquid, the more big then torque of liquid viscosity is bigger；Pass through survey
Determine torque size and obtains testing liquid viscosity number, unit mPas after conversion again.
Obtained effective silicon containing silicon composite fertilizer, effective calcium, effective magnesium, soluble alumina, soluble oxidation sodium content
Measurement according to Ministry of Agriculture professional standard NY T2272-2012《The measurement of soil conditioner silicon magnesium calcium content》、NY T 3035-
2016《The measurement of soil conditioner aluminium, nickel content》It executes.
Flyash comes from power plant of China of Inner Mongol ancient country of Shenhua, and concrete composition content is as shown in table 1.
Table 1
| Composition | Al2O3 | SiO2 | P2O5 | SO3 | K2O | CaO | TiO2 | Fe2O3 | MgO | Na2O |
| Content, weight % | 50.42 | 32.43 | 0.19 | 4.0 | 0.37 | 3.03 | 2.14 | 1.71 | 0.18 | 0.03 |
Flyash acid system residue of aluminum-extracted (white clay) carrys out autocollimatic Ge Er limited energies responsible company alumina producer, and preparation method can
With as follows：Flyash (power plant of China of Inner Mongol ancient country of Shenhua) 100g is taken, 12mol/L hydrochloric acid solutions are added, are stirred to react at 100 DEG C
30h, filtering obtain rich aluminum solutions and flyash acid system residue of aluminum-extracted after rinsing.Concrete composition content is as shown in table 2.
Table 2
| Composition | Al2O3 | SiO2 | P2O5 | SO3 | K2O | CaO | TiO2 | Fe2O3 | ZrO2 | Na2O |
| Content, weight % | 13.4 | 78.7 | 0.14 | 0.35 | 0.16 | 0.37 | 5.2 | 0.45 | 0.29 | - |
Embodiment 1
The preparation of silico-calcium composite fertilizer is carried out according to flow shown in FIG. 1.
(1) it takes white clay 3g that CaO powder 1.8g is added, the NaOH solution 20mL of 20 weight % concentration is added, stirs evenly, obtains
To reactant slurry.
(2) gained reactant slurry is transferred to and is warming up in 90 DEG C of reactor in advance, heat preservation 2h is reacted, and is reacted
It is kept stirring in journey, stir speed (S.S.) 80rpm；Reaction vessel is that the vessels not under pressure of silent form scatters and disappears to prevent moisture is too fast；Instead
Answer pressure close to normal pressure.
(3) it carries out being separated by solid-liquid separation after reaction and Washing of Filter Cake, reaction product viscosity is 3.2mPas.It filtrate and washes
Water amounts to 100mL, is concentrated by evaporation to 20mL, continues to employ to next batch and prepares reactant slurry；It is that silico-calcium is multiple after filter cake drying
Hefei product.Filter loss (entering filtrate and wash water) rate of Si elements is less than 0.3 weight %.
(4) gained silico-calcium complex fertilizer product is tested through analysis, available silicon content 27.18%, the active calcium ion content 37.56%,
Soluble Na2O content 2.39%.Product Na2O：SiO2Ratio=0.088.
It is 96.4% that NaOH, which recycles efficiency eta, in preparation process.
Embodiment 2
(1) it takes white clay 3g that CaO powder 1.8g is added, the NaOH solution 30mL of 13.3 weight % concentration is added, stirs evenly,
Obtain reactant slurry.
(2) gained reactant slurry is transferred to and is warming up in 100 DEG C of reactor in advance, heat preservation 3h is reacted, and is reacted
It is kept stirring in the process, stir speed (S.S.) 80rpm；Reaction vessel is that the vessels not under pressure of silent form scatters and disappears to prevent moisture is too fast；
Reaction pressure is close to normal pressure.
(3) it carries out being separated by solid-liquid separation after reaction and Washing of Filter Cake, reaction product viscosity is 2.2mPas.It filtrate and washes
Water amounts to 100mL, is concentrated by evaporation to 30mL, continues to employ to next batch and prepares reactant slurry；It is that silico-calcium is multiple after filter cake drying
Hefei product.Filter loss (entering filtrate and wash water) rate of Si elements is less than 0.5 weight %.
(4) gained silico-calcium complex fertilizer product is tested through analysis, available silicon content 37.86%, the active calcium ion content 35.44%,
Soluble Na2O content 4.69%.Product Na2O：SiO2Ratio=0.124.
Preparation process energy consumption is that recycle efficiency eta be 93.9% to middle NaOH.
Embodiment 3
(1) it takes white clay 3g that CaO powder 1.8g is added, the NaOH solution 60mL of 6.65 weight % concentration is added, stirs evenly,
Obtain reactant slurry.
(2) gained reactant slurry is transferred to and is warming up in 150 DEG C of reactor in advance, heat preservation 2h is reacted, and is reacted
It is kept stirring in the process, stir speed (S.S.) 80rpm；Reaction vessel is that the vessels not under pressure of silent form scatters and disappears to prevent moisture is too fast；
Reaction pressure is close to normal pressure.
(3) it carries out being separated by solid-liquid separation after reaction and Washing of Filter Cake, reaction product viscosity is 1.2mPas.It filtrate and washes
Water amounts to 100mL, is concentrated by evaporation to 60mL, continues to employ to next batch and prepares reactant slurry；It is that silico-calcium is multiple after filter cake drying
Hefei product.Filter loss (entering filtrate and wash water) rate of Si elements is less than 0.5 weight %.
(4) gained silico-calcium complex fertilizer product is tested through analysis, available silicon content 34.73%, the active calcium ion content 36.05%,
Soluble Na2O content 4.07%.Product Na2O：SiO2Ratio=0.113.
Preparation process energy consumption is that recycle efficiency eta be 94.6% to middle NaOH.
Embodiment 4
(1) it takes white clay 6g that CaO powder 3.2g is added, the NaOH solution 15mL of 20 weight % concentration is added, stirs evenly, obtains
To reactant slurry.
(2) gained reactant slurry is transferred to and is warming up in 100 DEG C of reactor in advance, heat preservation 3h is reacted, and is reacted
It is kept stirring in the process, stir speed (S.S.) 80rpm；Reaction vessel is that the vessels not under pressure of silent form scatters and disappears to prevent moisture is too fast；
Reaction pressure is close to normal pressure.
(3) it carries out being separated by solid-liquid separation after reaction and Washing of Filter Cake, reaction product viscosity is 3.1mPas.It filtrate and washes
Water amounts to 100mL, is concentrated by evaporation to 15mL, continues to employ to next batch and prepares reactant slurry；It is that silico-calcium is multiple after filter cake drying
Hefei product.Filter loss (entering filtrate and wash water) rate of Si elements is less than 0.5 weight %.
(4) gained silico-calcium complex fertilizer product is tested through analysis, available silicon content 32.33%, the active calcium ion content 35.36%,
Soluble Na2O content 3.76%.Product Na2O：SiO2Ratio=0.106.
Preparation process energy consumption is that recycle efficiency eta be 95.1% to middle NaOH..
Embodiment 5
(1) it takes white clay 9g that CaO powder 5.8g is added, the NaOH solution 60mL of 20 weight % concentration is added, stirs evenly, obtains
To reactant slurry.
(2) gained reactant slurry is transferred to and is warming up in 100 DEG C of reactor in advance, heat preservation 3.5h is reacted, instead
It should be kept stirring in the process, stir speed (S.S.) 80rpm；Reaction vessel is that the vessels not under pressure of silent form dissipates to prevent moisture is too fast
It loses；Reaction pressure is close to normal pressure.
(3) it carries out being separated by solid-liquid separation after reaction and Washing of Filter Cake, reaction product viscosity is 3.2mPas.It filtrate and washes
Water amounts to 900mL, is concentrated by evaporation to 60mL, continues to employ to next batch and prepares reactant slurry；It is that silico-calcium is multiple after filter cake drying
Hefei product.Filter loss (entering filtrate and wash water) rate of Si elements is less than 1.0 weight %.
(4) gained silico-calcium complex fertilizer product is tested through analysis, and available silicon content 36.0%, the active calcium ion content 32.7% can
Dissolubility Na2O content 4.89%.Product Na2O：SiO2Ratio=0.136.
Preparation process energy consumption is that recycle efficiency eta be 93.7% to middle NaOH..
Embodiment 6
(1) it takes white clay 400g that CaO powder 240g is added, the NaOH solution 3.0L of 17.8 weight % concentration is added, stirring is equal
It is even, obtain reactant slurry.
(2) gained reactant slurry is transferred to and is warming up in 100 DEG C of reactor in advance, heat preservation 3.0h is reacted, instead
It should be kept stirring in the process, stir speed (S.S.) 80rpm；Reaction vessel is that the vessels not under pressure of silent form dissipates to prevent moisture is too fast
It loses；Reaction pressure is close to normal pressure.
(3) it carries out being separated by solid-liquid separation after reaction and Washing of Filter Cake, reaction product viscosity is 2.8mPas.It filtrate and washes
Water amounts to 6.0L, is concentrated by evaporation to 3.0L, continues to employ to next batch and prepares reactant slurry；It is that silico-calcium is compound after filter cake drying
Fertilizer product.Filter loss (entering filtrate and wash water) rate of Si elements is less than 1.0 weight %.
(4) gained silico-calcium complex fertilizer product is tested through analysis, available silicon content 31.27%, the active calcium ion content 27.52%,
Soluble Na2O content 3.47%.Product Na2O：SiO2Ratio=0.11.
Preparation process energy consumption is that recycle efficiency eta be 95.5% to middle NaOH.
Embodiment 7
(1) it takes white clay 6g that CaO powder 2.0g is added, the NaOH solution 10mL of 20 weight % concentration is added, stirs evenly, obtains
To reactant slurry.
(2) gained reactant slurry is transferred to and is warming up in 100 DEG C of reactor in advance, heat preservation 3.0h is reacted, instead
It should be kept stirring in the process, stir speed (S.S.) 80rpm；Reaction vessel is that the vessels not under pressure of silent form dissipates to prevent moisture is too fast
It loses；Reaction pressure is close to normal pressure.
(3) it carries out being separated by solid-liquid separation after reaction and Washing of Filter Cake, reaction product viscosity is 3.4mPas.It filtrate and washes
Water amounts to 50mL, is concentrated by evaporation to 10mL, continues to employ to next batch and prepares reactant slurry；It is that silico-calcium is compound after filter cake drying
Fertilizer product.Filter loss (entering filtrate and wash water) rate of Si elements is less than 1.0 weight %.
(4) gained silico-calcium complex fertilizer product is tested through analysis, available silicon content 13.92%, is less than 20% standard value；Have
Imitate calcium content 25.92%, soluble Na2O content 6.89%.Product Na2O：SiO2Ratio=0.49.
Embodiment 8
(1) it takes white clay 9g that CaO powder 5.8g is added, the NaOH solution 60mL of 20 weight % concentration is added, stirs evenly, obtains
To reactant slurry.
(2) gained reactant slurry is transferred to and is warming up in 100 DEG C of reactor in advance, heat preservation 15h is reacted, and is reacted
It is kept stirring in the process, stir speed (S.S.) 80rpm；Reaction vessel is that the vessels not under pressure of silent form scatters and disappears to prevent moisture is too fast；
Reaction pressure is close to normal pressure.
(3) it carries out being separated by solid-liquid separation after reaction and Washing of Filter Cake, reaction product viscosity is 3.0mPas.It filtrate and washes
Water amounts to 900mL, is concentrated by evaporation to 60mL, continues to employ to next batch and prepares reactant slurry；It is that silico-calcium is multiple after filter cake drying
Hefei product.Filter loss (entering filtrate and wash water) rate of Si elements is less than 1.0 weight %.
(4) gained silico-calcium complex fertilizer product through analysis test, occur with rock-steady structure zeolite phase (it is not soluble in water or
Acid, aqueous slkali), relatively low available silicon content is only 16.2%, the active calcium ion content 28.9%, soluble Na2O content is up to
12.55%.Product Na2O：SiO2Ratio=0.77.
It is only 83.7% that NaOH, which recycles efficiency eta, in preparation process.
Comparative example 1
With flour mill by flyash acid system residue of aluminum-extracted grinding to 200 mesh hereinafter, then dilute with a concentration of 20 weight %
Hydrochloric acid, according to 1：The solid-liquid ratio of 3 (g/mL) is fully reacted, and product is filtered to obtain siliceous filter residue, this siliceous filter residue is dried
It is dry spare.It is spare in 120 DEG C of evaporative crystallizations to go out chloride containing calcium, the solid mixture of chlorination magnesium crystal for obtained filtrate simultaneously.It will
Spare siliceous filter residue with a concentration of 25% sodium hydroxide solution, by 1:The ratio of 1.5 (g/mL), is reacted at 80 DEG C,
Obtain liquid mixture containing sodium metasilicate.
Take weathered coal 50kg, urea 300kg, monoammonium phosphate 350kg, potassium chloride 250kg, bentonite 5kg, trace element fertilizer
Expect in the 10kg solid mixture 10kg of chlorination magnesium crystal (chloride containing calcium) input comminutors, 50kg is mixed containing sodium silicate liquid
Object is closed to be sprayed onto on above-mentioned bed of material by the fluid jetting head in comminutor, it is 4mm to be granulated to grain size, after drying, packaging
To containing silicon composite fertilizer.
It is tested through analysis, containing in silicon composite fertilizer, available silicon content is only 1.03 weight %, and the active calcium ion content is about 3 weights
Measure %, soluble Na2O content is 0.83 weight %.Product Na2O：SiO2Ratio=0.81.
Comparative example 2
(1) it takes white clay 3g that the NaOH solution 30mL of 20 weight % concentration is added, stirs evenly, obtain reactant slurry.
(2) gained reactant slurry is transferred to and is warming up in 110 DEG C of reactor in advance, heat preservation 2.5h is reacted, instead
It should be kept stirring in the process, stir speed (S.S.) 80rpm；Reaction vessel is that the vessels not under pressure of silent form dissipates to prevent moisture is too fast
It loses；Reaction pressure is close to normal pressure.
(3) it carries out being separated by solid-liquid separation after reaction and Washing of Filter Cake, reaction product viscosity is 16mPas.Filter cake contains inclined silicon
Sour sodium, it is sticky in paste, filtration difficulty, and be difficult to dry, filter loss (entering filter cake) rate of Si elements is all higher than 10 weights
Measure %.
(4) CaO powder of 1.8g is added in gained filtrate (main component sodium metasilicate), and advance heating is transferred to after stirring evenly
Into 90 DEG C of reactors, heat preservation 20min is reacted, and is kept stirring in reaction process, stir speed (S.S.) 80rpm；Reaction vessel
It is scattered and disappeared for the vessels not under pressure of silent form to prevent moisture is too fast；Reaction pressure is close to normal pressure.
(5) it carries out being separated by solid-liquid separation after reaction and Washing of Filter Cake, reaction product viscosity is 2.2mPas.It filtrate and washes
Water amounts to 50mL, is concentrated by evaporation to 20mL, continues to employ to next batch and prepares reactant slurry.
(6) filter cake dries to obtain silico-calcium composite fertilizer, and analysis test available silicon content only 18.75% is less than 20% standard value；
The active calcium ion content 39.18%, soluble Na2O content 4.65%.Product Na2O：SiO2Ratio=0.25.
Preparation process energy consumption is that middle NaOH recycles efficiency eta less than 85%.
Embodiment 9
Silicon-calcium-magnesium compound fertilizer preparation is carried out according to flow shown in Fig. 2.
(1) it takes white clay 3g that CaO powder 0.9g and MgO powder 0.64g is added, the NaOH solution of 6.67 weight % concentration is added
60mL is stirred evenly, and obtains reactant slurry.
(2) gained reactant slurry is transferred to and is warming up in 90 DEG C of reactor in advance, heat preservation 3h is reacted, and is reacted
It is kept stirring in journey, stir speed (S.S.) 80rpm；Reaction vessel is that the vessels not under pressure of silent form scatters and disappears to prevent moisture is too fast；Instead
Answer pressure close to normal pressure.
(3) it carries out being separated by solid-liquid separation after reaction and Washing of Filter Cake, reaction product viscosity is 2.4mPas.It filtrate and washes
Water amounts to 100mL, is concentrated by evaporation to 60mL, continues to employ to next batch and prepares reactant slurry；It is silicon-calcium-magnesium after filter cake drying
Complex fertilizer product.Filter loss (entering filtrate and wash water) rate of Si elements is less than 1.0 weight %.
(4) gained silicon-calcium-magnesium compound fertilizer product is tested through analysis, available silicon content 28.38%, the active calcium ion content
22.72%, effective content of magnesium 17.19%, soluble Na2O content 4.64%.Product Na2O：SiO2Ratio=0.16.
It is 96.1% that NaOH, which recycles efficiency eta, in preparation process.
Embodiment 10
(1) it takes white clay 3g that CaO powder 1.6g and MgO powder 0.14g is added, the NaOH solution of 20 weight % concentration is added
20mL is stirred evenly, and obtains reactant slurry.
(2) gained reactant slurry is transferred to and is warming up in 100 DEG C of reactor in advance, heat preservation 2h is reacted, and is reacted
It is kept stirring in the process, stir speed (S.S.) 80rpm；Reaction vessel is that the vessels not under pressure of silent form scatters and disappears to prevent moisture is too fast；
Reaction pressure is close to normal pressure.
(3) it carries out being separated by solid-liquid separation after reaction and Washing of Filter Cake, reaction product viscosity is 3.8mPas.It is easy to filter,
Filtrate and wash water amount to 100mL, are concentrated by evaporation to 20mL, continue to employ to next batch and prepare reactant slurry；After filter cake drying i.e.
For silicon-calcium-magnesium compound fertilizer product.Filter loss (entering filtrate and wash water) rate of Si elements is less than 1.0 weight %.
(4) gained silicon-calcium-magnesium compound fertilizer product is tested through analysis, available silicon content 36.20%, the active calcium ion content
28.64%, effective content of magnesium 5.44%, soluble Na2O content 4.60%.Product Na2O：SiO2Ratio=0.127.
Preparation process energy consumption is that recycle efficiency eta be 92.5% to middle NaOH.
Embodiment 11
(1) it takes white clay 3g that CaO powder 0.3g and MgO powder 1.07g is added, the NaOH solution of 13.3 weight % concentration is added
30mL is stirred evenly, and obtains reactant slurry.
(2) gained reactant slurry is transferred to and is warming up in 150 DEG C of reactor in advance, heat preservation 2h is reacted, and is reacted
It is kept stirring in the process, stir speed (S.S.) 80rpm；Reaction vessel is that the vessels not under pressure of silent form scatters and disappears to prevent moisture is too fast；
Reaction pressure is close to normal pressure.
(3) it carries out being separated by solid-liquid separation after reaction and Washing of Filter Cake, reaction product viscosity is 3.0mPas.It filtrate and washes
Water amounts to 100mL, is concentrated by evaporation to 30mL, continues to employ to next batch and prepares reactant slurry；It is silicon-calcium-magnesium after filter cake drying
Complex fertilizer product.Filter loss (entering filtrate and wash water) rate of Si elements is less than 1.0 weight %.
(4) gained silicon-calcium-magnesium compound fertilizer product is tested through analysis, available silicon content 26.55%, the active calcium ion content 5.35%,
Effective content of magnesium 19.10%, soluble Na2O content 3.25%.
Preparation process energy consumption is that recycle efficiency eta be 90.8% to middle NaOH.
Comparative example 3
(1) it takes white clay 3g that the NaOH solution 30mL of 20 weight % concentration is added, stirs evenly, obtain reactant slurry.
(2) gained reactant slurry is transferred to and is warming up in 140 DEG C of reactor in advance, heat preservation 1.5h is reacted, instead
It should be kept stirring in the process, stir speed (S.S.) 80rpm；Reaction vessel is that the vessels not under pressure of silent form dissipates to prevent moisture is too fast
It loses；Reaction pressure is close to normal pressure.
(3) it carries out being separated by solid-liquid separation after reaction and Washing of Filter Cake, reaction product viscosity is 16mPas.Filter cake contains inclined silicon
Sour sodium, it is sticky in paste, filtration difficulty, and be difficult to dry, filter loss (entering filter cake) rate of Si elements is all higher than 10 weights
Measure %.
(4) CaO powder 0.9g and MgO powder 0.64g is added in gained filtrate (main component sodium metasilicate), after stirring evenly
It is transferred to and is warming up in 60 DEG C of reactor in advance, heat preservation 1h is reacted, and is kept stirring in reaction process, stir speed (S.S.) 80rpm；
Reaction vessel is that the vessels not under pressure of silent form scatters and disappears to prevent moisture is too fast；Reaction pressure is close to normal pressure.
(5) it carries out being separated by solid-liquid separation after reaction and Washing of Filter Cake, reaction product viscosity is 2.2mPas.It filtrate and washes
Water amounts to 50mL, is concentrated by evaporation to 20mL, continues to employ to next batch and prepares reactant slurry.
(6) filter cake dries to obtain silicon-calcium-magnesium compound fertilizer, and analysis test available silicon content is 16.30%, is less than 20% standard
Value；The active calcium ion content 22.50%, effective content of magnesium 17.30%, soluble Na2O content 4.08%.Product Na2O：SiO2Ratio
=0.25.
Preparation process energy consumption is that middle NaOH recycles efficiency eta less than 85%.
Embodiment 12
Silicon magnesium compound fertilizer preparation is carried out according to flow shown in Fig. 3.
(1) it takes white clay 3g that MgO powder 1.29g are added, the NaOH solution 30mL of 20 weight % concentration is added, stirs evenly,
Obtain reactant slurry.
(2) gained reactant slurry is transferred to and is warming up in 120 DEG C of reactor in advance, heat preservation 3h is reacted, and is reacted
It is kept stirring in the process, stir speed (S.S.) 80rpm；Reaction vessel is that the vessels not under pressure of silent form scatters and disappears to prevent moisture is too fast；
Reaction pressure is close to normal pressure.
(3) it carries out being separated by solid-liquid separation after reaction and Washing of Filter Cake, reaction product viscosity is 3.4mPas.It filtrate and washes
Water amounts to 100mL, is concentrated by evaporation to 30mL, continues to employ to next batch and prepares reactant slurry；It is that silicon magnesium is multiple after filter cake drying
Hefei product.Filter loss (entering filtrate and wash water) rate of Si elements is less than 1.0%
(4) gained silicon magnesium compound fertilizer product is tested through analysis, available silicon content 21.94%, effective content of magnesium 39.34%,
Soluble Na2O content 2.64%.
Preparation process energy consumption is that recycle efficiency eta be 92.3% to middle NaOH.
Embodiment 13
(1) it takes white clay 3g that MgO powder 1.29g are added, the NaOH solution 60mL of 20 weight % concentration is added, stirs evenly,
Obtain reactant slurry.
(2) gained reactant slurry is transferred to and is warming up in 140 DEG C of reactor in advance, heat preservation 2h is reacted, and is reacted
It is kept stirring in the process, stir speed (S.S.) 80rpm；Reaction vessel is that the vessels not under pressure of silent form scatters and disappears to prevent moisture is too fast；
Reaction pressure is close to normal pressure.
(3) it carries out being separated by solid-liquid separation after reaction and Washing of Filter Cake, reaction product viscosity is 3.1mPas.It filtrate and washes
Water amounts to 100mL, is concentrated by evaporation to 60mL, continues to employ to next batch and prepares reactant slurry；It is that silicon magnesium is multiple after filter cake drying
Hefei product.Filter loss (entering filtrate and wash water) rate of Si elements is less than 1.0 weight %.
(4) gained silicon magnesium compound fertilizer product is tested through analysis, available silicon content 23.88%, effective content of magnesium 31.99%,
Soluble Na2O content 4.73%.
Preparation process energy consumption is that recycle efficiency eta be 92.0% to middle NaOH.
Embodiment 14
(1) it will take white clay 3g that MgO powder 1.29g are added, the NaOH solution 20mL of 20 weight % concentration is added, stirring is equal
It is even, obtain reactant slurry.
(2) gained reactant slurry is transferred to and is warming up in 160 DEG C of reactor in advance, heat preservation 5h is reacted, and is reacted
It is kept stirring in the process, stir speed (S.S.) 80rpm；Reaction vessel is that the vessels not under pressure of silent form scatters and disappears to prevent moisture is too fast；
Reaction pressure is close to normal pressure.
(3) it carries out being separated by solid-liquid separation after reaction and Washing of Filter Cake, reaction product viscosity is 3.0mPas.It filtrate and washes
Water amounts to 100mL, is concentrated by evaporation to 20mL, continues to employ to next batch and prepares reactant slurry；It is that silicon magnesium is multiple after filter cake drying
Hefei product.Filter loss (entering filtrate and wash water) rate of Si elements is less than 1.0 weight %.
(4) gained silicon magnesium compound fertilizer product is tested through analysis, available silicon content 30.50%, effective content of magnesium 31.98%,
Soluble Na2O content 8.12%.
Preparation process energy consumption is that recycle efficiency eta be 90.6% to middle NaOH.
Comparative example 4
(1) it takes white clay 3g that the NaOH solution 30mL of 20 weight % concentration is added, stirs evenly, obtain reactant slurry.
(2) gained reactant slurry is transferred to and is warming up in 120 DEG C of reactor in advance, heat preservation 2h is reacted, and is reacted
It is kept stirring in the process, stir speed (S.S.) 80rpm；Reaction vessel is that the vessels not under pressure of silent form scatters and disappears to prevent moisture is too fast；
Reaction pressure is close to normal pressure.
(3) it carries out being separated by solid-liquid separation after reaction and Washing of Filter Cake, reaction product viscosity is 15.5mPas.Filter cake is containing inclined
Sodium metasilicate, it is sticky in paste, filtration difficulty, and be difficult to dry, filter loss (entering filter cake) rate of Si elements is all higher than 10 weights
Measure %.
(4) MgO powder 1.29g are added in gained filtrate (main component sodium metasilicate), and advance heating is transferred to after stirring evenly
Into 20 DEG C of reactors, heat preservation 1.5h is reacted, and is kept stirring in reaction process, stir speed (S.S.) 80rpm；Reaction vessel is
The vessels not under pressure of silent form scatters and disappears to prevent moisture is too fast；Reaction pressure is close to normal pressure.
(5) it carries out being separated by solid-liquid separation after reaction and Washing of Filter Cake, reaction product viscosity is 2.2mPas.It filtrate and washes
Water amounts to 100mL, is concentrated by evaporation to 20mL, continues to employ to next batch and prepares reactant slurry.
(6) filter cake dries to obtain silicon magnesium compound fertilizer, and analysis test available silicon content only 11.94% is less than 20% standard value；
Effective content of magnesium 49.34%, soluble Na2O content 2.64%.
From the result of above-described embodiment and comparative example can be seen that method provided by the invention can effectively improve it is obtained
The amount retained containing soil nutrient elements in silicon composite fertilizer, available silicon content can be 21-38 weight %, effective magnesium in composite fertilizer
Content can be 5-40%, and the active calcium ion content can be 5-40%；Meanwhile the harmful solubility Al of agricultural2O3Content is less than 8%,
Soluble Na2O content is less than 6%.
Implement method provided by the invention, the low reaction product of viscosity can be obtained, avoids generating more difficult separation of solid and liquid
Sodium silicate solution.And involved in this method step the heating reaction can lower reaction temperature (90-160 DEG C),
Implement under shorter reaction time (2-5h) and normal pressure.The utilization ratio of white clay is 100%, and the NaOH solution used can recycle
It utilizes, loss is low and can reduce the discharge containing alkali waste water.
CaO and NaOH solution addition are not limited in the present invention in range in embodiment 7, the silico-calcium composite fertilizer caused
Middle available silicon content is less than the standard of 20 weight %.The reaction time is heated in embodiment 8 not in present invention restriction range, is caused
Available silicon content is less than standard in obtained silico-calcium composite fertilizer, and sodium element residual quantity is excessively high, and the rate of recovery of NaOH is low.
Comparative example 1 is the method for the prior art, and available silicon content is low in obtained composite fertilizer.Comparative example 2-4 is using existing
The method of technology generates sodium metasilicate in preparation process, and reaction product viscosity is big, and the loss of element silicon is big in filter process, silico-calcium,
Available silicon content is low in silicon-calcium-magnesium or silicon magnesium compound fertilizer.
In addition, method and process provided by the invention is extremely simple, equipment investment is small, and application range of products is wide, and the market space is big, competing
It is small to strive pressure, good environment and economic benefit can be generated.
Claims (10)
1. a kind of flyash acid system residue of aluminum-extracted prepares the method containing silicon composite fertilizer, including：
(1) in the presence of NaOH solution, flyash acid system residue of aluminum-extracted and the source of manure are mixed into slurries, and carry out heating reaction,
The wherein described source of manure is calcium source and/or magnesium source；
(2) reaction product that step (1) obtains is separated by solid-liquid separation, it is compound that gained filter cake obtains silico-calcium after being granulated, drying
Fertilizer, silicon magnesium compound fertilizer or silicon-calcium-magnesium compound fertilizer.
2. according to the method described in claim 1, wherein, when the source of manure is calcium source, the flyash acid system residue of aluminum-extracted with
SiO2Meter, the NaOH solution in terms of NaOH, the calcium source in terms of CaO, flyash acid system residue of aluminum-extracted, NaOH solution and calcium source
Weight ratio be 1：1.3-1.7：0.6-0.8.
3. according to the method described in claim 1, wherein, when the source of manure is calcium source and magnesium source, the flyash acid system carries aluminium
Residue is with SiO2Meter, the NaOH solution in terms of NaOH, the calcium source in terms of CaO, the magnesium source is in terms of MgO, flyash acid system
Residue of aluminum-extracted, NaOH solution, calcium source and the weight ratio in magnesium source are 1：1.3-1.7：0.1-0.6：0.4-0.04.
4. according to the method described in claim 1, wherein, when the source of manure is magnesium source, the flyash acid system residue of aluminum-extracted with
SiO2Meter, the NaOH solution in terms of NaOH, the magnesium source in terms of MgO, flyash acid system residue of aluminum-extracted, NaOH solution and magnesium source
Weight ratio be 1：1.5-1.8：0.5-0.7.
5. according to the method described in any one of claim 1-4, wherein heating reaction temperature is 90-160 DEG C, and heating is anti-
It is normal pressure to answer pressure, and the heating reaction time is 1-5h.
6. according to the method described in any one of claim 1-5, wherein this method further includes that the filter cake is carried out water
It washes, then will merge together concentrated rear return again containing the filtrate obtained by soda-wash water and the separation of solid and liquid obtained by the washing
The NaOH solution of step (1) is added.
7. according to the method described in claim 6, wherein, after the washing, sodium oxide content is 8 weight % in the filter cake
Below.
8. according to the method described in claim 1, wherein, viscosity of the reaction product at 25 DEG C described in step (2) is 1-
4mPa·s。
9. the method described in a kind of any one of claim 1-8 is obtained containing silicon composite fertilizer, wherein described to contain silicon composite fertilizer
Middle solubility Na2O content is 6 weight % or less；The silicon composite fertilizer that contains is that silico-calcium composite fertilizer, silicon magnesium compound fertilizer or silicon-calcium-magnesium are multiple
Hefei.
10. a kind of utilization method of flyash, including：Flyash progress acid system is carried that aluminium obtains aluminium oxide and flyash acid system carries
Silicon is prepared by the method described in any one of claim 1-8 in the flyash acid system residue of aluminum-extracted by residue of aluminum
Calcium composite fertilizer, silicon magnesium compound fertilizer or silicon-calcium-magnesium compound fertilizer.
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| WO2021203923A1 (en) * | 2020-04-09 | 2021-10-14 | 国家能源投资集团有限责任公司 | Liquid silicon-calcium fertilizer, preparation method therefor, and use thereof |
| CN113511924A (en) * | 2020-04-09 | 2021-10-19 | 国家能源投资集团有限责任公司 | Liquid calcium silicon fertilizer and preparation method and application thereof |
| CN113511924B (en) * | 2020-04-09 | 2022-10-11 | 国家能源投资集团有限责任公司 | Liquid calcium silicon fertilizer and preparation method and application thereof |
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